X-ray diffraction in polymer science

1) Identification of semicrystalline polymers and Recognition of

crystalline phases (polymorphism) of polymers

2)Polymers are never 100% crystalline. XRD is a primary technique

to determine the degree of crystallinity in polymers.

3) Microstructure: Crystallite size in polymers is usually on the nano-

scale in the thickness direction. The size of crystallites can be
determined using variants of the Scherrer equation.

4) Orientation: Polymers, due to their long chain structure, are highly

susceptible to orientation. XRD is a primary tool for the
determination of crystalline orientation through the Hermans
orientation function.
 1) Identification of semicrystalline polymers
Positions and Intensities of the peaks are used for identifying the material.
Unoriented PE
110
The diffraction of unoriented 2 = 21.4
I
samples in reflection
PE
polyethylene

200
2 = 23.9
The diffraction of unoriented samples in
transmission by using a flat film is characterized by 5 10 15 20 25 30 35 40
concentric circles called Debye Scherrer Rings 2 (deg)

110
Rhkl = D tan 2hkl =21.4)
(2

200
=23.9)
(2

Unoriented PE
 X ray diffraction of semicrystalline and amorphous
polymer

211
(20.3)
amorphous
I s-PS I s-PS
300
110 (11.8) syndiotattic syndiotactic
(6.2) polystyrene polystyrene
310
220
400
210

5 10 15 20 25 30 35 40 5 10 15 20 25 30 35 40
2 (deg) 2 (deg)
 1) Identification of crystalline phases of polymers
Position and Relative intensities are the fingerprint of crystalline phases of polymer

211

s-PS

110
220
a b
300
310 410
400 510
210
600
200
030
002
121 031
131

410 040
420
200
231
401
020 220
Intensity

210 041
331
020 _
210 410 132
111
_301
321

010 _101
111 _
421
_

411

_ _ 102
_
210 _230 112
321 _
302
211 322
301
020
210
111
_
121 121
_
421
_
411
220
030 212
_
_302
010 210 322 230
040
DCE

5 10 15 20 25 30 35 40
2 (deg)
Identification of crystalline phases of polymers also if they are present in mixture.

s-PS (110)I
i-PB

Intensity

(220)I
(211)I
tmax = 5 min

I (300)I

Tmax = 320 C
e Forma I

Tmax = 310 C
d Forma I + II

+
Tmax = 300 C
c Forma I + II
(200)II

Tmax = 290 C
b (311)II


(220)II

a Tmax = 280 C Forma II

0 5 10 15 20 25 30 35 40
2 (deg)
5 10 15 20 25 30
2 (deg)
X ray diffraction of semicrystalline polymer and inorganic
compound

inorganic compound
Polymer

211 I
(20.3) KBr
I
300 s-PS
110 (11.8) syndiotattic
(6.2) 310 polystyrene
220
400
210

5 10 15 20 25 30 35 40 45 50 55 60 65 70 75 80
5 10 15 20 25 30 35 40 2 (deg)

2 (deg)
 30000
What about this spectra?
9.5

25000

28.6
20000
Intensity (a.u.)

15000

10000
17

5000 19
18.6
14.1
25.6 48.7 59.3
21.6 38.5
0

5 10 15 20 25 30 35 40 45 50 55 60
2()
 Diffrazione dei raggi X del campione prima TGA

polimero

Diffrazione dei raggi X del campione dopo TGA

Carica inorganica
 The peak positions, intensities, widths and shapes
provide important information about the structure of the
material

amorphous / crystalline
(polymer, inorganic/organic compound)
crystalline phases
2)XRD a primary technique to determine the degree of crystallinity in polymers.

The determination of the degree of crystallinity implies use of a two-phase model, i.e. the
sample is composed of crystals and amorphous and no regions of semi-crystalline organization.

I = I crystalline + I amorphous

I
degree of crystallinity : xc

I crystalline
xc =
I crystalline + I amorphous
5 10 15 20 25 30 35

2
2) XRD : determination of degree of crystallinity in polymers.
The diffraction profile is divided in 2 parts: peaks are related to diffraction of crystallites,
broad alone is related to scattering of amorphous phase.

The assumption is that the areas are proportional to the

scattering intensities of crystalline and amorphous phases
Ia = diffracted intensity of
PE amorphous phase
Ib = diffracted intensity of
background
Ic Ic = diffracted intensity of
crystalline phase
Ia Ib
Acr
xc =
Acr + KAam

K is a constant related to the different scattering factors of crystalline and

amorphous phases. For relative measures K = 1.
 3) Microstructure: Crystallite size in polymers
The half-width of peaks is related to crystallite dimensions.

Half-width large correspond to smaller crystallites

Contribution to broadening can be due to

Intensity

lattice distortion, structural disorder as

well as instrumental effects.

5 10 15 20 25 30
2 (deg)

Half-width narrow correspond to bigger crystallites

Intensity

5 10 15 20 25 30
2 (deg)
 3) Microstructure: Crystallite size in polymers
Imax B = half-width of peaks
Intensity B = 2 = 22 21 =Bb
Imax/2 B
b = broadening instrumental
= broadening due to crystallites dimensions

2 b can be measured by the half-width of a peak

21 22 2 (deg) of crystalline compounds low molecular weight.

Crystallite size in polymers :

K
Lhkl = Scherrers Equation
cos
Lhkl = crystallite dimensions (in ) along the direction perpendicular to the
crystallographic plane hkl.
= half-width of peak related to the crystallographic plane hkl (rad).
K = constant (usually K = 0.89)
= diffraction angle of the hkl reflection.
= wavelength used ( Cuk = 1.5418 .)
4)Orientation: Polymers, due to their long chain structure,are highly susceptible to orientation

Fiber
axes

Draw direction

X-ray
c
fiber
X-ray diffraction of oriented polymer: fiber pattern

y meridian 360 x -1 y
cos 2 = cos cos tan
2 R R
Second layer l=2 (hk2)

First layer l=1 (hk1) l

c=
equator l=0 (hk0) sen(tan -1 ( y/R ))
x

c = periodicity along the chain axes

= wavelength used (CuK = 1.5418 )
l = layer
x, y = distance of reflections from the center
i-PP fiber along equatorial and meridian lines
R = chamber radius
X-ray diffraction of fibers annealed at different T

Distance from layers correspond to c axes

Helical
conformation
c=7.8

Trans-planar
conformation
c=5.1
Oriented sPP fiber stretched at different

First layer l=1 (hk1)

equator l=0 (hk0)

= 50 % = 100 % = 200 % = 500 %

=100(Lf-Li)/Li
Lf = final length
Li = initial length
The degree of orientation can be determined from the intensity
Z = draw axes
distribution of the corresponding diffraction on the Debye ring
by using the Hermans Orientation Function c
c,Z

f =
1
2
(3 cos 2 1) a,Z
b,Z
Azimutal scan: measuring the intensity at
2 constant, by varying the angle. Average cosine squared a b
value of angle

If the radiation is perpendicular to the fiber axes

cos 2hkl = cos 2 hkl

2 /2

I ( ) sen cos 2
d
< cos 2 hkl >= 0
/2

I()sen d
0

Orientation with respect to draw

direction If = 0 for meridian reflection (00l)
parameter parallel random perpendicular <cos200l> = 1 e fc = 1
<cos2> 1 1/3 0
f 1 0 -1/2 The fiber is perfected oriented: fc = 1
 Types of Orientation in polymers
Types of ORIENTATION GEOMETRY

(Heffelfinger Crystallographic Reference

PREFERRED ORIENTATION
& Burton)1 elements elements
1 Random - - -
Crystallographic Axes parallel
2 Axial c draw axes
to reference axes
Crystallographic Axes on a
3 Planar c film plane
reference plane
Crystallographic plane
4 Planar-axial (100) draw axes
Parallel to a reference axes
Crystallographic plane
5 Uniplanar (100) film plane
Parallel to a a reference plane

Crystallographic Axes parallel c draw axes

Uniplanar- to reference axes
6
axial and a Crystallographic plane
Parallel to a a reference plane (100) film plane

C. J. Heffelfinger, R. L. Burton J. Polym. Sci. 47, 289 (1960).

Uniplanar orientation: sps film
211 110 220
300

110 220
'' 211
510 410
300 310 410 200 400
400 210
600
200
210
101
600 002 E 040 E
040 111
041
131
150
150
020
130 060
120 130
''
060 101
020 110 111 240
110 240 170
140
170 D
030 031
002 D 020

Intensity
Intensity

121
410 131
040
_ 420 231
200
410 401

020 030
210 220 041
331 040
020 410
210 132
C C
111 _ 010
321
_
010 111 _
_ 411
_ 2_30
210 321 020
_
322 B 010
B
_
020 411
111 _
230
030 DCE clathrate DCE clathrate
_ _
010 210 111 020 111 030
302
040 A 040 A
5 10 15 20 25 30 35 40 5 10 15 20 25 30 35 40
2 (deg) 2 (deg)
Figure 2
Figure 1
 Types of Orientation in polymers
Through
direction

MD
End TD
direction Edge
direction

through end
Uniplanar orientation : (010)

010 edge

Rizzo, Lamberti, Albunia, Ruiz de Ballesteros, Guerra Macromol. 2002, 35, 5854
Albunia, Rizzo, Guerra Chem. Mat. 2009, 21,3370
 Along the chain projections of packing of forms of
s-PS showing (010) planes parallel to the film surface

Film surface

010 planes

8.70

(010) planes correspond to rows of parallel helices with minimum

interchain distances (8.70) and maximum interplanar distances
(10.56)
 s-PS co-crystals
a/2
L R 0.87 nm

a R
c L
R
b L

De Rosa, C.; Rizzo, P.; Ruiz de Ballesteros, O.; Petraccone, V.; Guerra G. Polymer, 1999, 40, 2103.
Chatani, Y.; Shimane, Y.; Inagaki, T.; Ijitsu, T.; Yukinari, T.; Shikuma, H. Polymer, 1993, 34, 1620.
 Unique feature of s-PS: three uniplanar orientations

a R Solvent induced crystallization

c L
R on amorphous film
b L
Bp < 110C Bp > 140C
Rizzo, Della Guardia, Guerra Rizzo, Spatola, Del Mauro, Guerra
Macromolecules 2004, 37, 8043 Macromolecules 2005, 38, 10089

a// c// a// c a c// Film

thickness

THF, CHCl3 p-xylene, dichloroethane Albunia, Rizzo, Tarallo, Petraccone,

Rizzo, Lamberti, Albunia, Ruiz, Guerra Rizzo, Costabile, Guerra Guerra Macromolecules 2008, 41, 8632
Macromolecules 2002, 35, 5854 Macromolecules 2004, 37, 3071

Solution casting; Spin-coating

 sPS Films: Orientation Upon Biaxial Balanced Drawing
E
biaxial D2
(sPS)syndiotactic polystyrene stretch
E I E
2.5x2.5 D1

E
a// c// L M R

Film surface

a a// c010
// Planes
planes

8.70

a// c// planes correspond to rows of parallel helices with minimum interchain
distances (8.70) and maximum interplanar distances (10.56)

Paola Rizzo*, Alexandra R. Albunia Macromolecular Chemistry and Physics 2011, 212,1419-26
 Uniplanar orientation
E
biaxial D2
stretch
E I E
2.5x2.5 D1

E
L M R

(PET) polyethylene terephthalate

(100) uniplanar orientation

(a=4.56 b=5.94 c=10.75 =98.5 =118 =112) triclinic lattice

Bin, Y.; Oishi,K.; Yoshida, K.; Nakashima T.; Matsuo, M.; J. Polymer, 2004, 36,394-402
 Uniplanar orientation
E
biaxial D2
stretch
(i-PP) polypropylene E I E
2.5x2.5 D1

E
L M R
A crystalline plane preferentially parallel to the film plane
Primary slip-plane:
- containing the chain axis
- and having the highest density

Paola Rizzo, Vincenzo Venditto, Gaetano Guerra, Antonio Vecchione Macromolecular Symposia 2002, 185, 53-63.
 Uniplanar orientation
biaxial
stretch
E
D2 A MD
E I E
2.5x2.5 D1

E (i-PP) polypropylene
L M R

B TD MD C
ND

TD
MD

Paola Rizzo, Vincenzo Venditto, Gaetano Guerra, Antonio Vecchione Macromolecular Symposia 2002, 185, 53-63.
In the Schulz reflection method the goniometer is set at the Bragg angle
corresponding to the crystallographic planes of interest. A special specimen holder
tilted the sample with the horizontal axis (y rotation axis), while rotating it in its own
plane about an axis normal to its surface (j rotation axis) . The y rotation can be
varied from 0to 90, whereas the j rotation can be varied from 0to 360. The pole
figures are plotted on a polar stereographic projection using linear intensity scale.
 Uniplanar orientation
E
D2
(i-PP) polypropylene
biaxial
stretch
E I E
2.5x2.5 D1 Iso-intensity lines indicate the relative
intensity of the pole related to the maximum
E diffracted intensity (assumed equal to 10).
L M R

The presence on the diffraction rings of the pole figures of the (110) and (130) reflection
of intensity maxima along MD indicates some preferential c-axis orientation along TD.
It is worth noting that this minor axial orientation, which is related to a not perfect
balancing of draw ratios between the two drawing directions.

Paola Rizzo, Vincenzo Venditto, Gaetano Guerra, Antonio Vecchione Macromolecular Symposia 2002, 185, 53-63.
iPP:uniplanar-axial orientation

A MD

B TD MD
C
ND

TD
MD

Paola Rizzo, Vincenzo Venditto, Gaetano Guerra, Antonio Vecchione Macromolecular Symposia 2002, 185, 53-63.
 iPP:uniplanar-axial orientation

The pole figure of the (040) reflection shows a strong maximum in ND. Correspondingly,
the (110) and (130) pole figures show rings at latitude 72 and 46, respectively.
These rings present more intense maxima along MD and less intense maxima along TD,
indicate the occurrence of a bimodal axial orientation, with prevailing orientation along TD.
Crystallites presenting (110) planes parallel to the film surface, associated with a c-axis
orientation along TD, can account for the two weak reflections at latitude of 72 along
MD, which are present on the (040) pole figure
Paola Rizzo, Vincenzo Venditto, Gaetano Guerra, Antonio Vecchione Macromolecular Symposia 2002, 185, 53-63.
 iPP:uniplanar-axial orientation

The bimodal axial orientation, associated

with a major uniplanar orientation relative
to the (0k0) planes and minor uniplanar
orientations relative to the (110) and (130)
planes, can rationalize all the diffraction
peaks which occur in photographic patterns,
like those shown previously

Paola Rizzo, Vincenzo Venditto, Gaetano Guerra, Antonio Vecchione Macromolecular Symposia 2002, 185, 53-63.
 Blown film of PE
(PE) polyethylene

a-axis (200) is preferentially oriented along the MD

It is evident that the a-axis (200) is preferentially oriented along the MD, because
poles with highest intensity are concentrated at the north and south ends of the (200)
pole figure.
In the (020) pole figure, poles with the highest intensity are concentrated in the center,
and spread along the TD. This suggests that b-axis is oriented in the ND-TD plane.

Chen, H. Y.; Bishop, M. T.; Landes, B. G.; Chum, S. P.; J. App. Polym. Sci., 2006, 101, 898-907
sPS:uniplanar-axial orientation
sPS:uniplanar-axial orientation

ac ax

a// c ax

cax
sPS: uniplanar-axial orientation